Novel large ring compounds

ABSTRACT

A series of mono, bi and tricarbocyclic compounds, most of which have olefinic unsaturation in the ring, which may or may not have substituents thereon. While the bi and tricyclic rings may be unsubstituted, these compounds which have olefinic unsaturation, particularly multiple olefinic unsaturation, are polymerizable and copolymerizable in known polymerization systems. They are particularly good crosslinking agents. These compounds are further useful in the sense that they can be cleaved oxidatively, to corresponding carboxylic acids, aldehydes and/or alcohols which have known utility in the plasticizer and detergent arts. The compounds which do not have olefinic unsaturation can also be oxidatively cleaved to produce oxygenated, e.g., acid, alcohol or aldehyde, compounds having known utility.

United States Patent [191 Wilke et al. v

[ 51 Nov. 18, 1975 1 NOVEL LARGE RING COMPOUNDS v [75] Inventors: Giinther Wilke; Paul Heimbach,

both of Mulheim (Ruhr); Germany [73] Assignee: Studiengesellschaft Kohle m.b.H.,

Mulheim (Ruhr), Germany [22] Filed: Apr. 22, 1974 [21] Appl. No.: 463,089

Related US. Application Data [60] Division of Ser. No. 109,949, Jan. 26, 1971, Pat. No.

3,849,506, which is a continuation of Ser. No. 843,220, July 18, 1969, Pat. No. 3,586,727, Ser. No. 845,901, July 29, 1969, Pat. No. 3,629,347, and'Ser. No. 845,904, July 29, 1969, Pat. No. 3,606,313, each is a continuationfin-part of Ser. No. 582,775, Sept. 27, 1966, abandoned.

[30] Foreign Application Priority Data Sept. 29, 1965 Germany 24439 [52] US. Cl. 260/666 PY; 260/666 B [51] Int. Cl. C07C 13/00 [58] Field of Search 260/666 PY [56] References Cited UNITED STATES PATENTS 2,964,574 12/1960 Wilke 260/66613 4/1961 Wilke et al.... 260/666 B 9/1962 Wilke 260/666 B ABSTRACT A series of mono, bi and tricarbocyclic compounds, most of which .have olefinic unsaturation in the ring, which may or may not have substituents thereon. While the bi and tricyclic rings may be unsubstituted, these compounds which have olefinic unsaturation, particularly multiple olefinic unsaturation, are polymerizable and copolymerizable in known polymerization systems. They are particularly good crosslinking agents. These compounds are further useful in the sense that they can be cleaved oxidatively, to corresponding carboxylicacids, aldehydes and/or alcohols which have known utility in the plasticizer and detergent arts. The compounds which do not have olefinic unsaturation canalso be oxidatively cleaved to produce oxygenated, e.g., acid, alcohol or aldehyde, compounds having known utility.

2 Claims, No Drawings NOVEL LARGE RING COMPOUNDS This application is a division of Ser. No. 109,949,

filed Jan. 26, 1971, now US. Pat. No. 3,849,506, which i in turn is a continuation of Ser. No. 843,220 of July 18, 1969, now U.S. Pat. No. 3,586,727; 845,901 of July 29, 1969, now US. Pat. No. 3,629,347 and Ser. No. 845,904 ofJuly 29, 1969, now US. Pat. No. 3,606,313, each of which in turn is a continuation-in-part of Ser. No. 582,775 of Sept. 27, 1966 now abandoned.

In these parent applications, a process has been described for the catalytic dimerization and trimerization, respectively, of 1,3-diolefins, in which catalysts are used which are produced by mixing carbonyl-free compounds of nickel with organometallic compounds such as metal alkyls, metal aryls, or Grignard compounds, or with metal hydrides or with metal hydride complex compounds and electron donors. The electron donors used are Lewis bases such as cyclic ethers, tertiary amines, especially cyclic tertiary amines, alkyl or aryl phosphines, especially triphenylphosphine, or alkyl or aryl phosphites or compounds with a carbon-to-carbon multiple bond. Similar processes are claimed in German Auslegeschrift No. 1,126,864 of Badische Anilinwherein:

When A is methyl and 6 is a cyclooctadiene,said

methyl is attached to a saturated carbon atom in The cyclo-cooligomerization of this invention can be performed with the aid of catalysts of zerovalent nickel such as those described in German Auslegeschrift No. 1,140,569 and in Austrian Pat. No. 232,495. These catalysts are especially well suited to use in the cyclocooligomerization of this invention since with these catalysts isomerizations of the types which have been observed to a certain extent in the case, for example, of catalysts prepared by means of alkali metals according to German Auslegeschrift No. 1,126,864 do not occur.

uhd Sedafabrlk, fh the Catalysts are made by the The carbonyl-free zerovalent nickel catalysts used in redhehoh of trahslhohal metal compounds y means of this invention have the additional advantage in the cymetals (Ah and Auslegesehhft clo-cooligomerization process thereof in that they are Whefem Certain f l-( Compounds e catalytically active at lower temperatures than, for exused as catalysts- Furthermore, It 1S kI10Wn that butadlample, the catalysts which are prepared according to ene can be transformed with the aid of catalysts, such G an Auslegeschrift No. 1,144,268. as 3 )2 Q)2 Into mlxhlres of eyeleoehfihege' The complex compounds of zerovalent nickel de- (115) h hvmyleyelohexehe by the metho S scribed m-German Auslegeschrlft No. 1, 191,375 can schhed In German 881,511 and also be used as catalysts. In all cases in which substif gg- A P N 232 495 th t tuted conjugated diene starting materials are used, the

eeor mg to Small e ea substituents themselves can be h drocarbons or funclytic co-oligomerization of butadiene and ethylene, for tional groups (e'gq alkoxy or cyarboxylic acid ester example, results in the fefmatioh of eyelodeeadlehe groups). They may also be hydrocarbons which contain h P Aeeerdmg to all the preeesses such functional groups. The only functional groups ine the ahovefelted P subshtuted 4O volved are those which do not enter into any reactions e h can h h lhstead of h with the catalysts, with the conjugated diene or other Th 1S f e lefor'the Pmduehoh of large mono, b1 reactants or with theunsaturated multlcyclic products OY y aheyehe rmgs of the formulai under the cyclo-coolig'omerization reaction conditions A. 6-B hereof. wherein: b

6 is a member selected from the group consisting of The Rroeess aeeordmg the Tvehheh g cyclooctadiene 1,5), cyclododecatriene (1,5,9) formed in the presence of nert scil vents, but on y t otse cyclodecadiene and cyclodecatriene; solvents WhlCh attack neither t ehreactants nor tl e A is a member selected from the group consisting of Products the catalystsil t e h i 3 methyl, ethyl, vinyl, phenyl, buten-l-yl, buten-Z-yl, components h the g g ydhldes whle We)? li f methoxy and carboalkoxy having up to 10 carbon for h achhe O t e Cate yet f h atoms and; phatic or aromatlc hydrocarbons, or aliphatic or cyclo- B is a member selected from the group consisting of ahphahe ethers are used Preferehhahy' hydrogen, methyl, ethyl, vinyl and a carboalkoxy of It is particularly advantageous, however, to use the up to 10 carbon atoms wherein: starting conjugated dlolefins or the products that can A and B can be linked together by a bridge of the forbe made according to the process of this invention as mula; solvents in the manufacture of the catalyst, so that a 1 H 1 or by the groups I' U- and an minimum of foreign substances will have to be separated from the reaction product. The process ofthis in vention can be performed at normal pressure of at elevated pressure. The pressure range in that case is determined by the desired direction of the reaction and by the temperature that is needed in each case. The process can be performed at temperatures from to 200C, but preferably at to 120C.

Multicyclic, unsaturated, hydrocarbon alicyclic rings can be produced according to the process of this invention in high yeilds with reference to the non-conjugated diene reactant. The compounds that can be manufactured according to the invention are valuable starting products for further syntheses. They can themselves be further cyclo-cooligomerized to higher molecular weight compounds which are resinous in nature and are therefore suited to use as molding materials. They can be hydrogenated to saturated compounds and as such used as solvents. They can be oxidatively cleaved at one or more unsaturated site to form aldehydes, alcohols or acids which are themselves useful in a manner and for applications known to be attributed to such functional groups.

Through the co-oligomerization of cyclic acetylenes with butadiene, 4,5-polymethylene-cyclodecatrienes- 1,4,7) can be produced in yields of more than 95 percent of the reacted cycloalkine:

wherein:

R, R, R", R' and R are each hydrogen or a substantially inert substituent such as an alkyl group, e.g., a lower alkyl group of up to about 8 carbon atoms, an aryl group, e.g., a mono or dicyclic phenyl or substituted phenyl moiety having up to about 16 carbon atoms, an alkoxy or aryloxy group or possibly one or more halo groups alone or on an alkyl, alkoxy or aryloxy group.

In an entirely analogous manner, one or more olefinically unsaturated rings (where the olefinic unsaturation is not or the conjugated diene type) cyclo-co-oligomerize with butadiene or a substituted butadiene to form an unsaturated multicyclic product.

In accordance with the practice of this invention the conjugated diene reactant or reactants are cyclo-cooligomerized with one or more cyclic non-benzenoid unsaturated compounds as olefins which are not conjugated dienes or as acetylenes in an reactant mole ratio such that there is preferably one mole of cyclic reactant to two moles of conjugated reactant. While these mole ratios are preferred, it will be clear to one skilled in this art that reactant proportions as low as 10 mole percent of one type of reactant to 90 mole percent of the other type of reactant are suited to use in this invention. Where more than one representative of either type of reactant is used, the individual compounds may be present in mole ratios of about 1 10 to 10 l with respect to each other where these are two reactants of one group. Where these are more than two reactants of a given group, each reactant should represent at least 10 mole percent of its entire group. It is preferred that 7 one conjugated diene react with one cyclic unsaturate in the above-recited mole ratio of about 2 1, respectively. 1

Another aspect of this invention is the cyclo-cooligomerization of at least one conjugated diene with an alkyl acrylate to form a lO-membered olefinically unsaturated alicyclic ring compound with a carboethoxy pendant group thereon.

It is surprising that the cyclo-cooligomerization proceeds very smoothly with very high conversions of the acrylic ester to the desired cyclic product with little or no attack on the carboalkoxy group and little or no conversion to open chain compounds. It is believed that this direction of the reaction is due to the particular catalyst being used. These catalysts are per se known materials and are themselves the subject of other patents and patent applications of one or both of the inventors hereof. These catalysts are defined as non-carbonyl-containing zerovalent nickel complex compounds. In particular, zerovalent nickel complexes of nickel with electron donors such as phosphines, phosphites, and multiple olefins are preferred. The reaction of this invention is schematically illustrated below:

o l/ RIC where R is an alkyl group, straight or branched chain, preferably having up to about 8 carbon atoms and wherein R R R and R are the same or different and may be hydrogen, alkyl, aryl, alkoxy, aryloxy, halo, haloalkyl, or the like. Alkyl, alkoxy, or haloalkyl groups suitably have up to about 8 carbon atoms in straight or branched chain configuration. Aryl or aryloxy groups suitably have one or two fused or unfused phenyl rings, preferably one, and may have one or several alkyl and- /or halo substituents on one or more of the rings.

Substituted 10 member rings can be produced by the process of the invention in high yields with reference to the acrylate reactant. The compounds that can be manufactured according to the invention are valuable starting products for further synthesis. The unsaturated cyclic products of this invention can be hydrogenated over 7 palladium or Raney nickel catalysts to large ring saturated alcohols which are useful as solvents and as starting materials for dehydrogenation or oxidation to cyclic ketones which are valuable perfume intermediates. The unsaturated cyclic products can be oxidatively cleaved to form di and tri carboxylic acid products which are useful as polyester and polyamide polymerization intermediates.

The following are illustrative of the, conjugated dienes which are ussful in this invention: butadiene, isoprene, piperylene, 'chloroprene, :ethyl butadiene, ethyl sorbate, phenylbutadiene, etc. Thefollowing are illustrative of the acrylates which are useful: methyl acry- 5 late, ethyl acrylate, n-butyl acrylate, 2-ethyl hexyl acrylate, acrylonitrile, etc. V i

The acrylate monomer and the conjugated diene monomer are suitably admixed in mole ratios of about 1 to [O l, preferably about l :2. Where different 10 conjugated dienes and different acrylates are cooligomerized, each member of the group should constitute at least about percent of its group. It is preferred that where several members of each group are used each be employed in substantially equal proportions.

Substituted l2-member rings are obtained, for example, by the simultaneous reaction of butadiene and iso prene in the presence of carbonyl-free catalysts of zero valent nickel. l-Methyl-cyclododecatriene-( 1,5,9) is formed to a major extent, along with a little dimethylcyclododecatriene-( 1,5,9), and some cyclododecatriene-( 1,5,9). I

-If butadiene is introduced into a solution of a catalyst nickel-(0) :tri-(O-phenyl)-phosphite =l l in isoprene;a substituted ring compound [l-methyl-cyclooctadiene-( l,5)] forms in yields closeto 90 percent of the reacted isoprene.

According to the invention, many different substituted 8, 10, and l2-member rings can be produced by cyclocooligomerization, according to the following reaction diagrams:

According to the invention, another type of cyclocooligomerization of l,3-diolefins can be achieved, namely, the cyclo-cooligomerization of l-disubstituted conjugated dienes with 2- or 2,3-disubstituted conjugateddienes.

W R R R R and R aryl or alkyl, or R and R H.

I Substituted 8,10, and lZ-member rings can be produced by the process of the invention in high yields with reference to the substituted butadiene-( 1,3) reactant. The compounds that can be manufactured according to the invention are valuable starting products for further synthesis. For example, l-substituted and l,2-disubstituted cyclooctadienes and cyclododecatrienes, as well as 4,5-dimethyl-cyclodecatrienes- 1,4,7) can easily be partially hydrogenated to form the corresponding l-disubstituted and 1,2-disubstituted cyclomonoolefins, respectively.

In addition to the cyclocooligomerization of two different conjugated dienes, such as butadiene and isoprene, according to this invention, another aspect of this invention resides in the cyclo-cooligomerization of two different conjugated dienes and an additional unsaturated copolymerizable monomer or monomers which additional monomer or monomers are acetylenically or olefinically unsaturated but are not themselves R R R5, R H or aryl, alkyl or alkoxy radicals; in

all of the above formulae at least one R is not hydrogen.

R R R R H or aryl, alkyl or alkoxy radicals; in

all of the above formulae atleast 1 R is not hydrogen.

conjugated dienes. Thus, according to this aspect of this invention, two or more different conjugated dienes, preferably two, are cyclo-cooligomerized under the same reaction conditions and catalyst as set forth above, with a monoolefinic or acetylenic comonomer to form a substituted alicyclic compound having at least 10 carbon atoms and at least two locations of unsaturation in the ring, and at least one substituent pendent from the ring.

The additional (third) monomer may be one or more of the following types of compounds: acetylene, substituted'acetylene, e.g., butine-l, ethylene, styrene, acrylonitrile, acrylic acid esters, and the like. The cyclocooligomerization, in this aspect of this invention the portion of the additional monomer pendent from the unsaturation therein, will form an additional pendent substituent on the alicyclic product. Thus, if butadiene, isoprene and propylene, for example, were cyclocooligomerized according to this invention, an alicyclic product having at least 10 carbon atoms in the rings, whether or not unsaturated, can be used as solvents.

Further, these unsaturated ring compounds can be oxidatively cleaved to .produce long-chain acids, aldehydes and alcohols which have known utility in the plasticizer and detergent arts.

' This invention will be illustrated by the following ex- EXAMPLE 1 4.34 g= 17.05 mmoles of nickel acetyl acetonate and 9.19 g 17.05 mmoles of tri-(o-phenylphenyl)- phospliite are reduced in 85 cc of benzene in'which about 10 g of butadiene are dissolved, with 4,43 g 34.1 mmoles of monoethoxydiethyl aluminum, at to 20C. In 2 hours approximately 250 g of butadiene per hour (total 680 g) are introduced into the catalyst solution at 60C over a period of about 2 hours and 40 minutes, with the simultaneous drop-by-drop addition of about 60 g of isoprene per hour (total 165 g). The reaction is interrupted, and distillation is performed directly from the reaction vessel at torr and a bath temperature of no more than 100C. 766 g of product are obtained, having the following compositions:

4-vinylcyclohexene mono-substituted 4winylcyclohexcnc p-diprcnc cyclooctudiene-( 1.5) l-methy1cyclooctudiene-( 1.5) dimethy1cyc1ooctadiene-( 1,5) c vc1ododecatriene( 1.5.9) 1-methylcyc1ododecatriene-( 1.5.9) dimethylcyclododecatriene-( 1.5 .9) trimethylcyclododecatriene-( 1.5.9)

EXAMPLE 2 The same catalyst was manufactured as described above, but in isoprene instead of benzene. For a period of 28 hours, at a reaction temperature that is slowly in creased from 30 to 52C, approximately g of butadiene per hour are introduced (total about 600 g butadiene). After distillation as in Example 1, 686 g of a product is obtained having the following composition:

4-vinylcyclohexene mono-substituted 4-vinylcyclohexene p-diprene cyclooctadiene-( 1.5) 1-methy1cyc1ooctadiene-( 1.5) dimethylcyclooctadiene-( 1 .5 cyc1ododecatriene-( 1,5,9) 1-methylcyc1ododecatriene-( 1.5.9) higher oligomers The yield of l-methylcyclooctadiene-( 1,5), with reference t0 reacted isoprene (approximately 21 percent transformation), amounts to about 84 percent of the theory.

EXAMPLE 3 Catalyst (twice the amount) and procedure as in Example 1. Instead of the phosphite, however, the corresponding amount (4.45 g) of triphenylphosphine is used. At a temperature of 60C approximately 30 g of butadiene per hour (total 250 g) are introduced into the catalyst solution and at the same time g of isoprene [per hour] is added in drop-by-drop fashion. After distillation as in Example 1, 36 2 g of product are obtained having the following composition:;

cy'clododecatriene 1 ,5.9)

I'm ethylcyclododecatriene-( 1.5 .9) dimethylcyclododecatriene-( 1.5.9)

trimethylcyclododecatriene-( 1 .5 ,9) higher oligomers The yield of l-methylcyclooctadiene-( 1,5), with reference to the reacted isoprene (37 percent transformation) amounts to 40 percent of the theory.

EXAMPLE 4 1.4% 4 vinylcyclohexene I 5.1 g 0.3% mono-substituted 4-viny1cycl0hexene 3.8 g 0.2% disubstituted 4-vinylcyclohexen 970.0 g 59.1% cyclooctadiene-(LS) 592.0 g 36.9% 3-methy1cyclooctadiene-(1.5) 44.0 g 2.6% dimethylcyclooctadiene-(1.5)

4.4 g 0.3% higher oligomers The yield of 3-methylcyclooctadiene-(1,5), with reference to the reacted piperylene (51 percent transformation), amounts to 86.4 percent of the theory.

EXAMPLE 5 Catalyst and procedure as in Example 1.

52 g of Z-phenyI-butadiene are placed in the reaction vessel and 50 g of butadiene per hour are introduced for 6 hours at C. After distillation, 342.4 g of product are obtained having the following composition:

9.5 g 2.8% 4-viny1cyc1ohexene 280.3 g 81.9% cyc1ooctadiene(1.5)

7.2 g 2.1% monosubstituted 4-vinylcyclohexene 42.2 g 12.3% 1-phenylcyclooctadiene-(1.5)

3.2 g 0.9% higher oligomers The yield of l-phenylcyclooctadiene-(1,5), with reference to the reacted 2-phenyl-butadiene (transformation 64 percent), amounts to 8 1 percent of the theory.

The l-phenylcyclooctadiene-(1,5) (B.P. C; 11,, 1,5764) can be hydrogenated catalytically in part to phenyl-cyclooctane (B.P. 149C; n 1.5319).

EXAMPLE 6 Catalyst and procedure as in Example 1.

60.1 g of l-methoxy-butadiene are heated to 60C together with the catalyst solution and for 20 hours approximately 30 g of butadiene per hour (total 620 g) are introduced. 661 g of a product are obtained having the following composition:

16.6 g I 2.5% 4-viny1cyc1ohexene 571.0 g 86.3% cyclooctadiene-( 1,5)

-continued 1.6 g 68.6 g 10.4% 3-methoxycyc1ooctadiene 1.5)

3.0g 015% higher oligomers The yield of 3-methoxycyclooctadiene-(1,5), with reference to the reacted l-methoxy-butadiene (transformation 85 percent), amounts to 94 percent of the theory. This 3-methoxycyclooctadiene-(1,5) B.P. 86C, n 1.4887) can easily be hydrogenated catalytically with the absorption of 2 moles of H to form the likewise previously undescribed methylcyclooctyl ether (B1 2 75 to 76C, n 1.4578). Both compounds were characterized by their infrared, H NMR and mass spectra.

EXAMPLE 7 Catalyst (1,5 times the amount) and procedure as in Example 1. The catalyst solution is mixed with 122 g of rnethy1-heptatriene-(1,3,6). At 60C, approximately 10 g of butadiene per hour were introduced for 28 hours (total about 290 g). 353 g are obtained of a product having the following composition:

6.0 g 1.7% 4vinylcyclohexene 238.0 g 67.5% cyclooctadiene-(l.5)

3.3 g 1.2% mono-substituted 4-vinylcyc1ohexene 105.2 g 29.8% 3-(butene-(1)-y1-(3)-cyc1ooctadiene- EXAMPLE 8 Catalyst and procedure as in Example 1.

77.2 g of 2,3-dimethyl-butadiene are heated to 60C together with the catalyst. For 16 hours, approximately 30 grams of butadiene per hour (total 460 g) is introduced, and 494.5 g of product is obtained having the following composition:

2.4% 4-viny1cyclohexene 85.9% cyclooctadiene-( 1,5)

10.2% l.2dimethyl-cyclooctadiene-( 1,5) 0.8% disubstituted 4-viny1cyclohexene 0.6% higher oligomers PP? cwaou: onoetmrmno 11 II II II II The yield of 1,Z-dimethyl-cyclooctadiene-(1,5), with reference to the reacted 2,3-dimethyl-butadiene (45 percent transformation), amounts to 93 percent of the theory.

The l,2-dimethyl-cyclooctadiene-(1,5) BR 785C, n 1.4941), which has not been described hitherto, can easily be hydrogenated, with Raney nickel as the catalyst, partially to l,2-dimethyl-cyclooctene,

0.2% mono-substituted 4- vinylcyclohexen'e g from which n-decadione-(2,9) (MP 63 to 64C) is obtained byoxidative decomposition.

EXAMPLE 9- Catalyst and procedure as in Example 1. 232 g ofn-octatriene-( 1,3,6) are heated with the cat alyst solution to C, with the introduction of butadiene. In 1.5 hours, approximately 400 g of butadiene are absorbed. 527 g of product are obtained having the following cornpositionz- 4-vinylcyc1ohexene cyclooctadiene-( 1.5) v monosubstituted 4-vinylcyc1ohexene 3-(butene-[2]-y1-[ l l )-cyclooctadiene- 1,5

EXAMPLE 10 The same catalyst as in Example 1 is reduced in a mixture of 340 g of piperylene and 432 g of isoprene with the addition of 17 g of butadiene, and the reaction mixture is heated for 96 hours in an autoclave at 55 to 57C. After distillation as in Example 1, 713 g of product are obtained having the following composition:

50.7 g 7.3% 5 unknown substance 14.4 g 2,l%; 3-methylcyclooctadiene-(1.5)

15.0 g 2.2% p-diprene 24.4g 3.5% l-methylcyclooctadiene-(1.5)

22.5 g 3.2% 6 unknown substance 70.2 g 10.1% dimethylcyclooctadiene-(1.5) (from piperylene) 68.2 g 9.7%

1,4-and 2.4-dimethy1 cyclooctadiene- 236.0g 34.1%. (1.5) 102.0 g 14.7% dimethylcyc1ooctadiene-(1.5) (from isoprene) 86.3 g 12.5% cyclic and open-chain trimers 3.5 g 0.5% higher oligomers.

EXAMPLE 1 1 4.34 g 17.05 mmoles of nickel acetyl acetonate are reduced in 380 g of piperylene with 4.43 g 34.1 mmoles of ethoxy aluminum diethyl. The catalyst solution is aspirated into an autoclave, and then 50 g of butadiene and 50 atmospheres of ethylene are forced in. Every two days another 50 g of butadiene are forced in. The reaction mixture is allowed to stand for 16 days at 12 to 15C. The excess ethylene and butadiene is blown off and then hydrogen is immediately forced in under pressure. After no more 1-1 absorption is to be observed even at 60C and 100 atmospheres hydrogen pressure, the autoclave is cooled and the excess gas is blown off, and the entire reaction product is distilled.

449 g of product are obtained, which, according to analysis by gas chromatography, has the following composition:

l.4% ethylcyclohexene 1.2% cyclooctune 5.4% n-decane 58.5% cyclodecane 22.1% methylcyclodecane 0.4% dimethylcyclodecane 0.3%

4.8% cyclododecane 3.7% higher oligomers The yield of methylcyclodecane (B.P. 92C) with reference to reacted piperylene (16 percent) amounts to about 75 percent.

EXAMPLE 12 The catalyst is prepared as in Example 11, but instead of piperylene 300 g of isoprene are used. The solution is aspirated into a 2-liter autoclave and mixed with 500 g of butadiene. The reaction mixture stands for five days at room temperature. After hydrogenation as in Example 1 l, 251 g of product are obtained, having the following composition:

0.6% ethylcyclohexune 0.6% '3 0.6% cyclooctane 9.4% n-decane 3.2% iso-undecane (methyldecune) 0.8% dimethyl-n-decane 60.0% cyclodeczme 15.9% methyl-cyclodecane 6.3% cyclododecane 0.8% methylcyclododecune 1.4% higher oligomers The yield of methyl-cyclododecane. with reference to the reacted isoprene (7 percent), amounts to about 72 percent of the theory.

EXAMPLE 13 ethylcyclohexane 1.2% n-decane 41.2% cyclooctane 10.0% methylcyclooctane 34.0% cyclodecane 9.5% methylcyclodecune 1.2% higher ollgomers flnrmnnnonn moo mna II II 11 11 II 1| II The yield of methylcyclooctane and methylcyclodecane, with reference to the reacted isoprene (about percent reacted), amounts to 91 percent of the theory.

EXAMPLE 14 18 g= 65.5 mmoles of Ni(cyc1ooctadiene-[ l,5]) are mixed in an autoclave with 1082 g of isoprene and 2000 g of butadiene and are allowed to stand for 2 months at 60C. After cooling, the catalyst in the reaction mixture is destroyed with 2N HCl with the admission of air. After distillation, 1383 g are obtained of a product of the following composition:

A portion of this product is hydrogenated, and by means of preparative gas chromatography methylcyclododecane is isolated (11 1.4718). The hitherto undescribed 1-methylcyclododecatriene-(1,5 ,9) 1 boils at 14.5 torr at 118C. (11 1.5048). The l-methylcyclododecatriene-( 1,5,9) 11 was characterized only by hydrogenation to methylcyclododecane.

The yeild of 1-methylcyclododecatriene-(1,5,9), with reference to reacted isoprene (27 percent reaction), amounts to 40 percent of the theory.

EXAMPLE l5 Catalyst and quantities of isoprene and butadiene as in Example 11.

The reaction mixture, however, is pumped through a reactor at l 10C with a time of stay of about 60 minutes, the reactor consisting of a copper capillary with a capacity of two liters which is lying in a heating bath and at the extremity of which there is installed a relie. valve adjusted 2050 atmospheres. Total time 2.5 hours. The composition of the products is similar to Example 14, but g of product is formed per hour per gram of nickel in the catalyst.

The yield of l-methyl-cyclododecatriene-( 1,5,9) amounts to 47 percent of the reacted isoprene (35 percent reacted).

EXAMPLE l6 Catalyst and procedure as in Example 14, but 1.08 kg of piperylene is used instead of isoprene. The reaction product obtained is agitated in air until it is virtually colorless. The nickel hydroxide that precipitates is separated by centrifugation and then distilled. 1514 g are obtained of a product having the following composition:

119.2 g 7.9% 4vin \'lcyclohexene 5.4 g 0.4% two unknown hydrocarbons 26.6 g 5.7%, cyclooctadiene-( 1.5)

1.7 g 0.1% 3-methyl-cyclooctadiene-(1.5) 73.7 g 4.8% five unknown hydrocarbons 1057.3 g 69.8% cyclododecatriene 130.0 g 8.6% 3-methyLcyclododecatriene-( 1.5.9)

40.0 g 2.6% higher oligomers The yield of 3-methyl-cyclododecatrienee( 1,5,9), with reference to reacted piperylene (2 9. percent reacted) amounts to 53 percent of the theory. v In the distillation, a 3-methyl-cyclododecatriene- (1,5,9) is obtained (8.1 105C, n 1.4968, 92 percent pure) which still has a tcc-cyclododecatriene- (1,5,9)-content of 8 percent. Catalytic hydrogenation yields methyl-cyclododecane in addition to cyclododecane.

EXAMPLE 17 Catalyst as in Example 1. After the addition of 100 g of 20 ethylbutadiene, the mixture is heated to 60C and for 2 hours approximately 250 g of butadiene are introduced per hour. After distillation as in Example 1, the following is obtained:

4-vinylcyclohexene cyclooc tadiene-( 1,5)

g ethyl-substituted 4-vinylcyclohexene g g 10 l-ethyl-cyclooctadiene-( l .5)

g diethy1cyclooctadiene-( 1.5) 0.6 g cyclododecatriene-( 1.5.9) 2.3 g higher hydrocarbons 564.9 g product The yield of '1-ethyl-cyclooctadiene-( 1,5 with reference to reacted ethylbutadiene (approximately 70 percent reacted), amounts to 95 percent of the theory.

1-ethyl cyclooctadiene-(1,5), which has not been described hitherto, (B.P. 76C, n 1,4900), was characterized by infrared, H NMR and mass spectroscopy.

EXAMPLE l8 Catalyst as in Example 1, but half the amount. At 80C, butadiene is introduced into the catalyst solution and simultaneously 55 g of sorbic acid ethyl ester is added drop by drop over a period of 2 hours. As the drop-by-drop addition is made, the catalyst turns deep red and the butadiene absorption becomes slower. In hours approximately 320 g of butadiene are reacted. After the usual distillation, the following is obtained:

7.5 g 2.2% 4-vinylcyclohexene 293.0 g 85.9% cyclooctadiene-(LS) 3.9 g 1.1% six-ring codimers of butadiene and sorbic acid ethyl ester 32.2 g 9.4% (8-methyl-cyclooctadienyl-(3)-carboxylic acid ethyl ester [1] 4.7 g 1.4% higher olefins The yield of [1] amounts to 85 percent of the reacted sorbic acid ethyl ester (amount reacted 50 percent).

The 8-methyl-cyclooctadienyl( 1 ,5 3 )-carboxylic acid ethyl ester (B.P. 133C, n 1.484), which has not been described previously, was characterized by infrared, H NMR and mass spectra.

EXAMPLE 19 The catalyst was prepared by reducing 4.34 g 17.05 mmoles of nickel acetyl acetonate and 9.19 g 17.05 mmoles of tri-(o-phenyl phenyl)-phosphite in 85 cc of benzene, in which about 10 g of butadiene are dissolved, with 4.43 g 34.1 mmoles of monoethoxydiethyl aluminum at 0 to 20C.

This catalyst solution was heated together with 1 14 g of cyclododecine to 40C, and then for 20 hours, about g of butadiene per hour were fed in. Thereafter all volatile components of the reaction mixture were distilled out at 10 torr and up to 40C. The distillation residue, which contained the catalyst in addition to the higher-boiling hydrocarbon product, was dissolved in 300 ml of pentane. The catalyst was destroyed by treatment with 2 N HCl and excess air. The product of catalyst destruction, tri-(o-phenyl-phenyl) phosphite, is substantially insoluble in pentane and was removed from the pentane solution by suction filtration. The resultant solution was cooled and concentrated to yield:

4-vinylcyclohexene cyclooctadiene-( 1.5)

unknown C to C range compound bi-cyclo-( 10.8.0 )-eicosatriene-( cis. cis, trans/3 3.7)

higher oligomers having a melting point of 635 to 64C. The melting point of the bicycloeicosatriene was 89 to 94C, depending upon the rapidity of heating, because of the rearrangement thereof to a cis-divinylcyclohexene system. This rearrangement is observed in the case of all cyclodeca-(1,5)-dienes and cyclodeca-( 1,4,7) trienes. At higher temperatures the rearrangement is to 3,4- divinyl-bicyclo-(10,4,0)-hexadecene-(cis-A which is partially hydrogenated to 3,4-diethyl-bicyclo-(10,4,0)- hexadecene-(cis-A which has a boiling point of 135 to 139C at 10 torr and a refraction index n,, of 1.5045.

EXAMPLE 20 Approximately 200 g of butadiene are introduced per hour into the catalyst solution prepared according to Example 1, at to C for a period of 3 hours. At the same time, approximately 70 g of bicyc1o-(2,2,1)-heptene-(2) are added drop by drop. After vacuum distillation according to Example 1, 636 g of product are obtained, having the following composition:

4-vinylcyclohexene cyclooctadiene-( 1.5) cyclododecatriene-( 1.5.9) two unknown hydrocarbons tricyc1o-( 10.210 penta decudiene-(cis. trans-4.8)

9295? 000000 "QOQOQUQOQ This tricyclopentadecadiene partially isomerizes at high temperature to form cis-4,S-divinyl-tricyclo- (6,2,1,0 )-undecane (B.P. 147C, n 1.5120). Hydrogenation with the absorption of 2 moles of hydrogen produces the corresponding cis-diethyl compound (B.P. 153C, n 1,4934). Upon catalytic hydrogenation over platinum in glacial acetic acid, the tricyclopentadecadiene (M.P. 19.5 to 20C) yields tricyclo-(10,2,1,0 ')-pentadecane (8.1

All of the hitherto undescribed compounds were EXAMPLE 21 The catalyst was prepared as in Example 1. 36 g 191 mm of cyclotetradecadiine( 1,8) were added to the catalyst solution and approximately 50 g of butadiene per hour were introduced at 40C over about 25 hours. All of the volatiles (benzene, 4-vinylocyclohexene, cyclooctadiene-(1,5)) were removed by vacuum distillation at 0.1 torr and 20C. Approximately 500 ml of benzene were added to the distillation residue. The tricyclo(20,8,0" 0 )-triacontahexaene- (A"3,7,A ,l8,22) (I) that was formed is practically insoluble in benzene and therefore can be removed by filtration. The catalyst was destroyed by shaking the benzene solution with 2N aqueous l-lCl solution and with excess air. After drying with calcined Na SO,, the benzene was distilled off at reduced pressure. The residue was taken up in a little pentane, whereupon the tri- (o-phenylphenyl)-phosphate, being insoluble, is left behind. After the pentane is removed by distillation, bicyclo-(12,8,0)-eicosatriene(A ,3,7)-ine-(l6) (I1) and unreacted cyclotetradecadiine are separated by fractional crystallization from an ether alcohol mixture. The following product distribution was obtained:

35.5 g 2.77: 4-\'inylcyclohexene 1218.0 g 94.271 cyclooctadiene-(LS) 14.8 g 1.2% (11) 15.2 g 1.2% (1) 10.0 g 0.8% higher oligomers and residue.

Substances (I) and (11) were formed in a yield of 93 percent with reference to the cyclotetradecadiine that reacted (conversion 45 percent).

Substance (1) has a melting point of l60164C, and Substance (II) has a melting point of 98101C. Substances (1) and (11) have been characterized by H NMR and infrared spectra. The partial hydrogenation 16 of Substance (I) yields Tricyclo-(2,0,8,O,O triacontadiene-(A A and the partial hydrogenation of Substance (11) yields bicyclo-(12,8,0)-doco- 1,10 sene-(A EXAMPLE 22 The catalyst was prepared by reducing 4.34 g 17.05 mmoles of nickel acetyl acetonate and 9.19 g 17.05 mmoles of tri-(o-phenylphenyl)-phosphite in cc of benzene, in which about 10 g of butadiene are dissolved, with 4.43 g 34.1 mmoles of monoethoxy diethyl aluminum at 0 to 20C. After the addition of 34 g of acrylic acid ethyl ester, approximately 25 g of butadiene were introduced at 60C for 20 hours. After the customary distillation, the following is obtained after hydrogenation;

6.3 g 2.171 ethylcyclohexene 233.8 g 79.07 cyclooctane 17.8 g 6.0% cyclodecanecarboxylic acid ethyl ester 27 g 0.97: undecanic acid ethyl ester 35.3 g 11.9% residue.

EXAMPLE 23 1.9% ethylcyclohexane 86.67: cyclooctane 9.0% cyclodecunecarbox \'lic acid ester 0.57: (cis-3.4-diethyl-cyclohexenyl)- carboxylic acid ethyl ester 1.1% undecanic acid ethyl ester 1.0% residue and higher oligomers What is claimed is: l. Bicyclo (10, 8, O) Eicosadiene cis 1 cis trans 2. Tricyclo (10, 2, 1, 0 penta decadiene (cis,

-UNITED STATES PATENT AND TRADEMARK OFFICE (IERTIFICATE 0F CORRECTION PATENT NO. 3,920,762

DATED 1 November 18, 1975 |N\/ENTOR(S) Gunther Wilke et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[60], line 5, delete "Pat. No. 3,606,313" and insert abandoned Column 5, line 24, "(O-phenyl)" should read (O-phenylphenyl) q Column 12, line 31, "yeild" should read yield Column 16, line 1, "2,0" should read 2O Signed and Scaled this Twentieth Day of July 1976 [SEAL] A ttes t:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'Patenrs and Trademarks 

1. BICYCLO (10,8,0) EICOSADIENE CIS 1 CIS TRANS 1.10, 3,7.
 2. Tricyclo (10, 2, 1, 0 2, 11) pentadecadiene (cis, trans 4, 8). 